Curable sealant composition

ABSTRACT

A radiation curable, flexible, paintable composition produced from epoxy compounds and one or more polyol(s) has enhanced durability, thick and thin film adhesion, resistance to mold growth and dimensional changes while reducing solvent emissions. The composition can reduce, if not eliminate, runs and drips during the thermal bake cycles which are associated with using conventional compositions in automotive applications.

CROSS REFERENCE TO RELATED PATENT APPLICATIONS

This is a continuation in part of U.S. patent application Ser. No.09/197,107, now U.S. Pat. No. 6,277,898 filed on Nov. 20, 1998 that isin turn a continuation in part of Ser. No. 09/081,966, filed on May 20,1998, now U.S. Pat. No. 6,174,932 and entitled “Curable SealantComposition”. The disclosure of these prior filed patent applications ishereby incorporated by reference.

The subject matter herein also claims benefit under 35 U.S.C. 111(a), 35U.S.C. 119(e) and 35 U.S.C. 120 of U.S. Provisional Patent ApplicationSerial No. 60/047,290, filed on May 21, 1997, entitled “A UV-CurableSealant Compositions”; and U.S. Provisional Patent Application SerialNo. 60/079,204, filed on Mar. 24, 1998, entitled“Radiation CurableSealant Compositions”. The disclosure of the aforementioned ProvisionalPatent Applications is hereby incorporated by reference.

The subject matter of the instant invention is also related to copendingand commonly assigned Non-Provisional U.S. patent application Ser. No.09/344,198, filed on Jun. 24, 1999, Ser. No. 09/300,930, filed on Apr.28, 1999, Ser. No. 09/081,967, filed on May 20, 1998 and Ser. No.09/197,124, filed on Nov. 20, 1998 and entitled “Novel FoamingComposition and Methods for Making and Using the Compositions”. Thedisclosure of these commonly assigned patent applications is herebyincorporated by reference.

FIELD OF THE INVENTION

The invention relates to a curable composition, methods for applying thecomposition as well as end-uses for the cured composition

BACKGROUND OF THE INVENTION

Sealants are employed in a wide range of applications. For example, theautomotive industry employs sealants between and upon metal seams andwelds, within hollow cavities to impart structural and sound dampingcharacteristics, among other locations.

One specific sealant environment involves the use of a sealant upon thewelds in the so-called “roof-ditch” which is formed when joining theside panels of the body to the roof of the vehicle. The roof-ditch weldis conventionally covered with a bead or strip of polyvinyl chloride(PVC) based molding that is typically covered with a metal strip andpainted. The PVC strip typically contains plasticizers, stabilizers,lubricants, among other compounds that can volatilize from the stripthereby causing cracking and shrinking. When the PVC strip cracks suchcan reduce the effectiveness of the strip and in turn allow theunderlying metal to corrode.

Conventional sealants including those employed in roof ditches can alsocreate conditions which are conducive to microbial, e.g., fungal,growth; especially in warm humid environments. The microbe growth occursbecause the sealant contains substances that can be metabolized by themicrobe. Consequently, there is a need in the sealant industry for asealant with enhanced durability, and microbial resistance and cosmeticvalue that can be applied in an expedient manner. There is also a needin this industry for a sealant that can be repaired or replaced.

Methods for applying and curing/heating coatings are described in U.S.Pat. No. 4,844,947 (Kasner et al.), U.S. Pat. No. 5,348,604 (Neff) andU.S. Pat. No. 5,453,451 (Sokol). The disclosure of the previouslyidentified patents is hereby incorporated by reference in their entiretyfor all purposes.

SUMMARY OF THE INVENTION

This invention is capable of solving problems associated withconventional practices by providing a radiation curable composition,which can be employed as a sealant that is easy to manipulate, durable,paintable, repairable/replaceable, crack and microbe resistant, e.g.,mildew.

The inventive composition can be employed in a wide range ofenvironments including in the automotive industry, e.g., as a roof-ditchsealant. The composition of the invention can be applied by usingcommercially available dispensing equipment, e.g., brushing, dipping,spraying or pumping, and cured in-situ, e.g., by a source of energy orradiation such as UV radiation, electron beam, laser, microwave, amongother energy sources sufficient to cause curing sufficient to controlsag or material flow for a specific application. If desired, theinventive composition can be painted.

In one aspect, the curable composition according to this inventioncomprises at least one epoxy compound, at least one carrier, e.g.,polyol, and at least one suitable photoinitiators. In addition, thecurable composition can optionally include at least one thickener orfiller, as well as at least one monomers and/or at least one phenoxyresins. In one embodiment, the inventive composition can comprise: 1) atleast one epoxy such as that supplied by UCB Radcure as Uvacure 1500,1530, and 1534 or by Sartomer as SARCAT K126, 2) at least one andpreferably two or more polyols such as the polyester polyols supplied byUnion Carbide as Tone 0301 and by Huls America as Dynacoll 7110, 3) atleast one photoinitiator such as sulfonium salt supplied by UnionCarbide as Cyracure UVI 6974 and by Sartomer as CD1010; and optionally,the following additional three components, 4) at least one thickener orfiller such as silicon dioxide supplied by Cabot Corporation and 5) atleast one monomer such as TONE M-100 also supplied by Union Carbide, ahydroxy polyester acrylate/hydroxyethyl acrylate blend or a monomer suchas caprolactone acrylate supplied by Sartomer; and 6) at least onephenoxy resin such as phenoxy resin such as phenoxy resin PKHP 200supplied by Phenoxy Specialties.

In another aspect, the curable composition is pre-initiated beforecontacting the substrate. By “pre-initiated”, “pre-initiating” or“pre-initiate(s)” it is meant exposure to a suitable source of energy orradiation at least once: 1) while combining the components of thecomposition, 2) when preparing at least one component of the compositionprior to combining with other components, 3) during transport of thecomposition or components thereof through a conduit or related handlingequipment, among other suitable techniques to pre-initiate curing of thecomposition. If desired, the composition can be pre-initiated by aradiation source that is embedded or located within or upon a conduit orother member such that radiation can be supplied to the composition orcomponents thereof, e.g, UV radiation is shown through a window on aconduit that delivers the composition to a substrate. The radiationsource may also be embedded within the system for dispensing thecomposition, e.g., a UV source located within a nozzle that applies thecomposition onto a substrate. Pre-initiating the curable compositionpermits controlling the viscosity of the composition as well as reducingthe curing time after being applied onto a substrate.

These and other aspects of the invention will become apparent from thespecification and claims which follows.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a schematic drawing of an apparatus that can be used forapplying the inventive composition by using robotic means.

FIG. 2 is a schematic drawing of the apparatus illustrated in FIG. 1 asthe inventive composition is applied.

DETAILED DESCRIPTION

A first aspect of the invention relates to a radiation curablecomposition comprising at least one epoxy, epoxy based compounds andepoxy functional or modified compounds, at least one carrier, e.g.,polyols, and at least one photo-initiator.

The first of the components employed in the curable compositioncomprises an epoxy compound. While any suitable epoxy and epoxyfunctional compounds (or mixtures thereof) can be employed in theinventive composition, a curable liquid cationic epoxy compound and, inparticular, a cycloaliphatic epoxy compound is preferred. Specificexamples of suitable epoxy compounds comprise those materials suppliedby UCB Radcure as Uvacure 1500, 1530, and 1534 or by Sartomer as SARCATK126. Normally, the epoxy corresponds to about 40 to about 90 wt. % andpreferably about 45 to about 60 wt. % of the composition prior tocuring.

Without wishing to be bound by any theory or explanation, it is believedthat the inventive composition employs a cationic reaction that can bephotoinitiated, that continues as a cascade reaction; especially ifheated. It is also believed that when the inventive composition isexposed to a source of suitable radiation, e.g., UV energy, a relativelythin “skin”forms substantially instantaneously upon the surface of thecomposition. This surface skin serves to stabilize the shape of thecomposition until the remainder of the composition has reacted, e.g.,cross-linked, into a self-supporting structure. The thickness of theskin as well as the resultant article can be tailored to satisfy aparticular end-use, e.g, an article having a thickness of from about0.05 to at least about 10 mm as well as forming a skin upon anunderlying uncured material.

While not necessary to obtain a useful composition, the effectiveness ofthe aforementioned epoxy compound is enhanced by the second component ofthe composition, at least one polyol. While it is believed that anypolyol recognized in the art can be suitably employed in the invention,examples of preferred polyols comprise polyether polyols and polyesterpolyols such as those supplied commercially by manufacturers such asUnion Carbide, Huls America and Arco. Specific examples includepolyester polyols supplied by Union Carbide as Tone 0301 and by HulsAmerica as Dynacoll 7110. The amount of polyol in the composition priorto curing preferably ranges from about 5 to about 50 wt. %, morepreferably 10-25 wt. %.

Moreover, the epoxy to polyol ratio can range from about 1:1 to about2:1. The use of more than one polyol is desired. By employing more thanone polyol, the properties of the inventive composition can be moreeffectively controlled. Examples of properties that can be tailoredinclude glass transition point, viscosity, adhesion to the underlyingsubstrate (e.g., in the case of a roof ditch the automotive E-coat),degree of cross-linking in the cured composition, flexibility, amongother desirable properties.

A photoinitiator is employed in the composition when using UV radiationfor inducing an interaction among one or more components of the curablecomposition, typically the epoxy and polyol. The amount ofphotoinitiator normally corresponds to about 0.5 to about 2 wt. % of thecomposition prior to curing. While any suitable photoinitiator ormixtures thereof can be employed, UV photoinitiators are preferred. Inparticular, desirable results have been obtained by using a onium saltssuch as sulfonium salt, triarylsulfonium hexafluoroantimonate,diaryliodonium hexafluoroantimonate, and mixtures thereof, among others.Specific examples of suitable sulfonium salts include those supplied byUnion Carbide as Cyracure UVI 6974 and by Sartomer as CD1010.

In another aspect of the invention, the photo initiator can be partiallyor completely replaced by an acid source such a Lewis acid. Examples ofsuitable Lewis acids include sulfonic acids, phosphoric acid, citricacid, carboxylic acid, tannic and oxalic acids, and mixtures thereof,among others. Normally, better results are obtained by using a source ofphosphoric acid. In this aspect of the invention, the composition isemployed in a two component system with the epoxy compound and the acidsource being separately maintained until it is desirable to produce aself-supporting coating or an article. When the epoxy and acid arecontacted a reaction occurs providing a product similar to the onedescribed herein when a photoinitiator is used. The amount of acidnormally corresponds to about 0.25% to about 3.0% wt. % of thecomposition prior to curing. The epoxy and/or acid can be admixed withother components of the inventive composition, e.g., the acid can beadmixed with a polyol.

The ingredients of the two component system can be combined by using anyart recognized mixing technique while ensuring that two components aresegregated prior to usage. The components can be contacted either byhand in a suitable container, or dispensed through a commerciallyavailable static mixing tube and simultaneously applying the resultingfluid onto the substrate in question.

The curable compositions according to the invention can include otheroptional components depending on, among other factors, the ultimate enduse of the cured material. To this end, at least one thickener or fillercan be included as an optional component of the inventive composition.The amount of thickener normally corresponds to about 0.5 to about 5.0wt. % of the composition prior to curing. While any suitable thickenercan be employed fumed or aerosol silica can be used to obtain desirableresults, e.g., fumed silicas commercially supplied by Cabot Corporation(M-5 Grade) and Degussa. Normally, precipitated silica is not employed.

The thickener is typically non-reactive and employed to create athixotropic fluid, e.g., having a viscosity of about 20,000 to about80,000 centipoise. Consequently, the thickener can be introduced intothe composition in any expedient manner, e.g., added to the polyol andvacuum mixed. If desired, the thickener can comprise a treated silicasuch as a silica having a silane surface treatment, e.g., TS720 suppliedby Cabot Corporation.

The viscosity of the composition or components thereof can also bemodified by exposure to a radiation source, e.g., by pre-initiating thecomposition. Exposure to a radiation source causes at least a portion ofthe composition or components thereof to cure thereby causing anincreased viscosity.

In addition, the curable composition can include a monomer component tofacilitate formation of the cured material. Examples of suitablemonomeric materials comprise acrylates, caprolatones, polycarbonates,and mixtures thereof, among others. The amount of monomer typicallycomprises about 1 to about 5 % by wt. of the composition prior tocuring. Without wishing to be bound by any theory or explanation, it isbelieved that the monomer component functions as a cross-linking agentduring curing.

Yet other additives can also be included in the curable composition.Depending upon the inventive composition and particular end-use of asubstrate which is coated with the inventive composition, suitableadditives can comprise: bis-F epoxy, thickeners, fillers such as carbonblack, polyproplyene, proplyene carbonate, calcium carbonate,microspheres (such as Micropearl, supplied by Pierce & Stevens, Corp.);surfactants, pH indicators, biocides/antifungal compounds, solvents,fire extinguishants, silanes, pigments, UV stabilizers, PVC, PTFE,resins such as ethylene-vinyl acetate co-polymers, among other compoundswhich do not adversely impact curing.

The additives should be selected so as to not effect transmission of thecuring radiation. For example, when employing a UV curable system, bestresults are obtained by avoiding materials that affect UV lighttransmission. Because of this, the two component system and systemsactivated by an electron beam or other energy sources can include awider range of materials such as dyes, pigments, UV light stabilizers,among others. While any suitable pigment can be employed, specificexamples of pigments comprise at least one member selected from thegroup consisting of E2557 Green, E6824 Yellow, E4102 Red, 626 blue (allsupplied by Akrochem) mixtures thereof, among others. Examples ofsuitable UV 1 stabilizers comprise at least one member of Oxalanilideclass, mixtures thereof, among others. The amount of such additives, ifpresent, normally comprises about 0.1 to about 2.0 wt. % of thecomposition, prior to curing.

If desired, the inventive composition can include fibers, platelets,particles, among other components in order to form a composite article.Typically, the amount of such additives will range from about 1 to about15 wt percent of composition prior to curing. Normally, it is desirableto minimize the presence of basic materials and/or those that affect UVtransmittance when a UV curable system is employed.

The uncured composition can be provided by any suitable means foradmixing or combining the components of the composition. Normally, atleast one of the epoxy or polyol will be heated to a temperature that iseffective for increasing the rate at which the thickener, e.g., silica,can be dispersed. Bubbles formed during the mixing process can beremoved by pulling a vacuum on the mixture. Greater details regardingthe mixing process can be found in the forthcoming Examples.

A specific example of a curable composition according to this inventioncomprises the following:

TABLE 1 Chemical Name Trade Name Supplier Wt. % Cycloaliphatic EpoxyUvacure 1500 UCB Radcure 25-45 Polyester Polyol Tone 0301 Union Carbide 0-45 Polyester Polyol Dynacoll 7110 Huls America 10-35 HydroxyPolyester Tone M-100 Union Carbide 10-35 Acrylate/Hydroxyethyl AcrylateSilicon Dioxide Cab-O-Sil Cabot   0-8.0 Sulfonium Salt* Cyracure UVI6974 Union Carbide 0.5-3.0 *50 wt. % propylene carbonate

The inventive composition can be applied and cured effectively atambient temperatures, e.g., about 65 about 95° F., thereby obviating theneed to heat the composition during application. In some cases, however,it may be desirable to monitor and control the curing temperature ifambient temperatures are extreme. By obviating the requirement for heatcuring, the instant invention permits utilization of unheated dispensingequipment as well as application upon unheated substrates.

The particular substrate is not critical to the invention and clearlydepends on the end use for the cured materials. Examples of suitablesubstrates can comprise one or more of steel, stainless steel,galvanized surfaces, surfaces having a coating such as E-coat, paint,among a virtually unlimited array of substrates. While heating is notnecessary to apply the composition, once applied the cured compositioncan be baked or heated for improving the adhesion of the composition tothe underlying substrate. For example, a source of infrared energy canbe employed in combination with a source of UV or electron beamradiation, e.g., a UV lamp.

Curing of the inventive composition can be initiated via a source ofradiation suitable for activating the photoinitiator. Since the use ofUV curable initiators is preferred, the preferred radiation sourceprovides ultraviolet radiation (UV). To this end, while curing can beinitiated by naturally occurring UV light, normally, a man-made sourceof UV radiation is employed, e.g, to cross-link the polymeric matrix.The source of UV radiation can range widely such as a lamp mounted abovea conveyor, a lamp mounted on a robot arm, a series of lamps mounted ina gantry located above or adjacent to a robot that dispenses thecomposition, among other apparatus for supplying UV radiation.

After applying the inventive composition upon a suitable substrate, thecomposition can be exposed to a high output source of energy, e.g., UVradiation (approx 2.5 J/cm² @ 365 nm, which may vary with exposure time,distance from source and type of bulb), that initiates curing therebylocking or freezing the composition as a coating upon the substrate. Thespecific wavelength of UV can be tailored to satisfy a wide range ofproduct uses, exposure times and distance from the composition to becured; but, normally ranges from greater than about 250 to about 400 nmand having an output of about 2.5 to about 4.0 J/cm². In some cases, itis desirable to employ one or more UV sources that emit differing UVwavelengths either simultaneously or sequentially, e.g., lamps that emitdiffering wavelengths and/or by one type of lamp having a filter.Examples of suitable UV curing systems and lamps are Model F600 System,“D”, “V” and “H” lamps all of which are supplied by Fusion SystemsCorporation, Rockville, Md.

The radiation exposure time of the inventive composition is typicallyabout 1 to about 10 seconds. The specific exposure time can be tailoreddepending upon the distance from the radiation source, intensity of thesource, relative speed between the composition to be cured and theradiation source, among other parameters. As described above, the sourceof, e.g., UV radiation, can be supplied by any suitable means such as aconveyor, UV lamp such as a Fusion Systems “H” bulb attached to orassociated with an arm of a robot which dispenses uncured composition,e.g., as a bead within a roof ditch or a spray upon a substrate.Consequently, the inventive composition can be readily employed inconventional fabrication or manufacturing processes. Typically, a safetycurtain or booth, which surrounds the radiation source, is desirable forminimizing any impact upon personnel. When the composition is employedin automotive applications such as a roof ditch, the radiation (UV)curing step can be followed by a thermal bake, which enhances formationof a permanent adhesive bond to the underlying surface, e.g., anelectrocoat (E-Coat), and improves the final curing of the sealant'spolymer matrix. The thermal bake is typically conducted at a temperaturegreater than about 340 ° F. and less than that which adversely impactsthe coated substrate. While a thermal bake is not required for allapplications of the inventive compositions, such a thermal bake canenhance the adhesion between the inventive composition and theunderlying surface, and if desired can be employed in conjunction withradiation (UV) exposure.

The inventive composition also has the ability to cure with ultravioletrays from the sun. While the sun can be employed as a source of UVradiation, the cure time is relatively long in comparison to curing withconcentrated/high energy UV sources. Examples of applications that canemploy natural UV curing include the building/construction industry suchas roof panel joints for metal building, skylight seals, concrete/cementsealants, drywall joint-compound (“mud”), among other applicationsexposed to natural UV radiation. For example, the inventive compositioncan be applied or sprayed upon concrete/cement and cured in natural UVto form a water-proof paintable coating, e.g., an interior or exteriorbasement sealant and a swimming pool liner or seal.

Subsequent operations to the coated substrate will typically not disturbthe coating, e.g., when the coating is employed as an automotive roofditch sealant the coating will not drip or run during subsequentmanufacturing steps such as painting. The long term dimensionalstability of the cured inventive composition is improved in comparisonto conventional PVC sealant compositions, e.g., no cracks or shrinkagebecome evident during UV exposure and repeated thermal bakes orenvironmental exposures. When shrinkage was measured substantially inaccordance with ASTM D2453, the inventive composition had a shrinkage ofabout 0% when measured visually.

The inventive composition is a high cosmetic paintable material (aso-called Class A automotive). With proper application, the sealantprovides excellent smoothness and gloss retention, e.g., the inventivesealant does not adversely impact the distinctiveness of image (DOI) ofan overlying paint. When deposited within a channel or groove the curedcomposition typically forms a reverse miniscus, or “U-shaped” crosssection. Such a configuration reduces paint cracking; especially whenthe inventive composition is employed for sealing automotive roofditches.

The inventive composition possesses an improved adhesion to conventionalpaint systems such as standard solvent based pigmented and clearsystems, water based, latex, powder paints, automotive E-coats, mixturesthereof, among others. The inventive composition also possesses adesirable resistance to the ambient environment, e.g., twelve monthFlorida exposure testing in accordance with conventional testing methodshas proven the inventive composition's durability as well as itsresistance to mold/mildew growth, cracking and chalking. The inventivecomposition is also resistant to paint staining, fading and cracking asa result of Xenon Arc exposure.

The chemistry of the inventive composition allows the composition to betailored to possess a wide variety of physical characteristics. Byutilizing the constituent ratios of the composition, the physicalcharacteristics of the cured product will range from a flexible andrelatively soft article to a hard sandable product. Thesecharacteristics can be obtained by varying the epoxy to polyol weightratio e.g., the ratio can range from about 2:1 to about 4:1. Normally,an increased amount of epoxy will correspond to a harder cured coating.When the composition contains relatively large quantities of polyol, thehardness of the cured coating is reduced upon exposure to moisture, e.g,the Shore “A” Hardness when determined in accordance with conventionalmeasuring techniques ranges from about 70 to at least about 95. Thepresence of relatively large quantities of polyol can, however, improveadhesion of the inventive composition to the underlying substrate.

The hardness of the composition can be increased by including ahardening resin such as a phenoxy resin. While any suitable hardeningresin can be employed, examples of suitable resins comprise at least onemember selected from the group consisting of phenoxy resin, solid epoxy(in particulate form), mixtures thereof, among others. Normally, theamount of hardening resin corresponds to about 1 to about 9 wt. % of thecomposition prior to curing. By including such a hardening resin, theShore “D” hardness of the composition, subsequent to curing, can rangefrom about 60 to about 80. The hardening resin also improves the solventand moisture resistance of the cured composition.

In addition, the viscosity of an uncured composition can be tailored byadjusting the silica to polymer ratio and/or the polyol ratio. Theviscosity of the uncured composition can also be increased byintroducing a solid epoxy in addition to or as a replacement for theaforementioned epoxies. Examples of suitable solid epoxies comprisebis-phenol A, novalac resin, mixtures thereof, among others. Theviscosity can be tailored to be similar to paint, or increased to agrease or paste-like consistency. The presence of a solid epoxy can alsobe employed for imparting enhanced resistance to moisture.

The inventive composition, prior to curing, is typically greater that 95wt. %, preferably, about 98.5 to at least about 99.75 wt. % solids,e.g., about 99.5 wt. % solids. While the dimensional thickness of theinventive composition can be tailored to satisfy a wide range ofend-uses, normally the composition is applied at a thickness of about0.05 mm to about 10 mm thick, e.g., in the case of roof ditch thecomposition is about 5 mm thick. The ability of the inventivecomposition to form such relatively thick layers is in contrast toconventional practices and a marked improvement.

While the inventive composition is not adversely affected by mostsolvents, the composition can substantially reduce, if not eliminate,the presence of solvents, e.g., the inventive composition can beessentially volatile organic compound (VOC) free. The inventive can alsobe substantially free of polyvinyl chlorides and its monomers. That is,the uncured composition may include about 0.1 to about 5.0 wt. %,normally about 0.5 wt. %, of solvents and/or PVCs, e.g., a solvent whichfunctions as a carrier for the photoinitiator, e.g., about 0.50 wt. %propylene carbonate.

As described above, the inventive radiation cured composition can beemployed in a wide range of applications; especially in the automotivefield. One such example comprises a roof ditch sealant which is a ClassA paintable sealer. Once the inventive composition is applied, thecomposition is cured in situ by a source of concentrated UV lightthereby permitting an “in-line” curing application. That is, a roboticarm can be a double functional tool, with both a dispensing nozzle fordelivering the inventive composition into a roof ditch and the curinglamp attached in parallel. Alternatively, the curing lamp(s), e.g, oneor more UV and infrared lamps, can be physically separate butoperationally connected to the robot, e.g., the lamps are mounted aboveor beside the robot on a gantry wherein the movement/operation of therobot and lamps are controlled by computer. The inventive compositioncan be supplied to the robot arm by using any suitable pump such as apositive displacement reciprocating piston pump, e.g., Model No.711008-662-000 5 gal. pump supplied by Graco Inc.

In one particular aspect of the aforementioned roof ditch application, aplurality of protrusions, studs or mechanical fastening means having anydesirable shape can be located within and attached to the bottom of theditch for enhancing the bond between the ditch and overlying radiationcured composition. When studs are employed, the studs can be weldedwithin the ditch when forming the underlying weld that forms the ditch,e.g, when welding the automotive roof and side body panels together. Anyprotrusions can also be affixed within the ditch by a suitable adhesive,or by mechanical attachment. The height and specific configuration ofthe protrusions depends upon the application; but, normally, theprotrusions are about 3 to about 7 mm tall. These protrusions can befabricated from any suitable material such as thermoplastics such asnylon, metal, among other materials. When introduced into the ditch, theinventive flowing composition embeds the protrusions, fills the ditchand can form a self-leveling surface. These protrusions can also beutilized in after-market applications when repairing or replacing a roofditch sealant.

The configuration of the roof ditch can be tailored for improving themechanical bond between the ditch and radiation cured composition. Forexample, a ditch having trapezoidal cross-section can be employed. Ifdesired, the previously described protrusions or studs can be employedwithin a tailored ditch configuration.

The inventive composition can also be applied upon non-planar surfaces.For example, the inventive composition can be employed as a Class Apaintable automotive coach and coach joint sealant. Such joints can beon a horizontal or vertical surface. The ability of the inventivecomposition to be cured substantially simultaneously followingapplication permits the composition to be employed on such verticalsurfaces. In order to enhance vertical surface application, theviscosity of the inventive composition can be increased by adding about3 to about 10 wt. % of a thickener such as CAB-O-SIL silica, elastomermodified or adducted epoxy, polyether polyol, mixtures thereof, amongothers.

Moreover, the inventive composition can be employed for repairing dentsand scratches in a painted surface, e.g., an automotive door. That is,the composition can be applied upon a surface, exposed to a radiationsource such as UV light, and, thereafter, sanded as needed and paintedin accordance with conventional methods. Similarly, a two componentsystem can be employed without using exposure to a radiation source. Forexample, a two component system based upon an interaction between anepoxy and acid can be combined, applied upon a surface as a gel,permitted,to harden and adhere to the surface and, thereafter, preparedfor painting by using conventional techniques. In some cases, thesubstrate being repaired and/or inventive composition can be heated toenhance adhesion to the substrate.

The inventive composition can be applied onto a wide range ofsubstrates. The inventive composition can be employed in a method forapplying one or more coatings upon an automotive surface. For example,an automotive assembly may be immersed within the inventive compositionand, thereafter, cured by being exposed to radiation. Such an immersionmay be employed, for example, as an enhancement or a replacement forconventional automotive E-coats. Once cured, the automotive assembly canbe painted in accordance with conventional methods. Without wishing tobe bound by any theory or explanation, it is believed that thecomposition may be tailored for application upon unpainted surfaces as acorrosion protectant, e.g., sprayed upon an automotive underbody, amongother applications.

In one aspect of the invention, the inventive composition can beemployed as an automotive brake rotor coating for imparting corrosionprotection. The inventive composition can be applied via an aerosol or aspray upon the rotor to form a thin film coating. The resultant layer issacrificial in that the layer is consumed or removed when contacted bythe brake pad. In a related aspect, the inventive composition can beemployed as a temporary corrosion protectant such as upon saw bladeswherein friction or other usage of the protected article removes thecoating. In such cases, it can be useful to add one or more surfactants,e.g., less than about 1.0 wt. % of Fluorad FC-171 fluorochemicalavailable from 3M.

In another aspect of the invention, the inventive coating is employed asa Class B paintable coating. For example, the inventive coating isapplied as a spray upon a painted or unpainted metal substrate such alower automotive body panel in order to form an anti-chip coating(so-called stoneguard). The inventive composition can also be sprayedupon the floor pan, roof, among other regions of an automobile duringassembly for improving acoustics, among other properties.

In another aspect of the invention, the inventive composition can bemixed, molded, extruded or shaped into an article that is subsequentlyexposed to a radiation source. If desired, the inventive composition canbe co-extruded with another material thereby forming an article having aradiation curable surface. While a wide range of articles can be formed,one example of such an article comprises automotive moldings. Suchmoldings can be fabricated and shipped to an automotive assembly plant,or extruded and cured directly on the automobile.

Moreover, the inventive composition can be shaped into hollow spheres orother continuous surfaces by being shaped while being exposed to asource of radiation. The inventive composition can be sprayed/spraydried in a conventional manner while being exposed to radiation. Theresultant spheres or product can be employed alone or incorporated intoanother matrix to obtain a composite. Similarly, the inventivecomposition can be cast into a film or web.

In a further aspect of the invention, the inventive composition isemployed as a repair material for automotive coatings, seals, householdapplications, among other areas wherein it is desirable to havelong-lasting, flexible and paintable sealants. For example, theinventive composition can be applied upon a substrate, cured withradiation and exposed to infrared (IR) radiation for 90 seconds therebyforming a seal to repair a crack in the underlying substrate or coating.

In a still further aspect of the invention, the inventive compositioncan be employed as a top-coating upon a wide range of articles includingfasteners, end-fittings, couplings, among others. These articles can beimmersed within the inventive composition, centrifuged (so-calleddip-spin processing), and exposed to a radiation source thereby curingthe composition and forming a durable outer or top-coating upon thearticles.

The previously described curable compositions can be modified to obtaina gel consistency by adding a gelling agent. Examples of suitablegelling agents include treated or untreated silica, detergents,elastomer modified or adducted epoxy, polyether polyols, mixturesthereof, among others. When using a UV curable composition, the gellingagent should not adversely affect UV transmission through thecomposition. The gelling agent normally comprises about 0.5 to about 10wt. % of an uncured compositions. By employing a gelling agent, theviscosity and handling characteristics of the inventive composition canbe improved, e.g, the composition can be tailored to possess a putty orcaulk-like consistency.

Moreover, the curable compositions can be modified to obtain an acid orradiation activated foam. Any suitable chemical or mechanical expansionagent can be added to these compositions. Examples of suitable chemicalor mechanical expansion agent include water, hydrazide,diphenyloxide-4,4-disulphohydrazide, hexamethylene diamine carbamate,carbonamide, azocarbonamide, sodium bicarbonate, carbon dioxide,fluorocarbons, encapsulated materials, e.g, Expancel supplied by H. M.Royal; mixtures thereof, among others. The expansion agent normallycomprises about 0.5 to about 10 wt. % of an uncured compositions. Theexpansion agent becomes activated by being exposed to either UV or asuitable source of heat, e.g, an exothermic reaction between an epoxyand acid source. For example, when employing a UV curable compositionand such a composition is exposed to UV light an exothermic reactionoccurs that in turn causes the expansion agent to swell therebyincreasing the volume of the composition. Similarly, when an acidactivated composition is employed, the heat released when the acidcontacts the epoxy causes the expansion agent to swell. Radiationactivated foams are described in greater detail in copending andcommonly assigned U.S. patent application Ser. No. 09/344,198, filed onJun. 24, 1999 and entitled “Novel Foaming Composition and Methods forMaking and Using the Composition”; the disclosure of which is herebyincorporated by reference.

While the above description places particular emphasis upon applying theinventive composition within an automotive roof ditch, the inventivecomposition can be applied to a wide range of substrates. Examples ofsuitable substrates include at least one member of the group consistingof metals such as stainless steel, galvanized steel, concrete, cement,glass, wood, among others. In the case of metal substrates, theinventive composition can be applied upon a welded joint including ajoint formed by spot, wire and laser welding.

The composition of the instant invention can be applied to a substrateby any suitable method. Such methods include brushing, immersing,pumping, dipping, painting, spraying, among other suitable conventionalmethods. When the inventive composition is applied upon the weld in anautomotive roof ditch, it is desirable to pump the composition into andalong the ditch. Because of its low viscosity at, for example, at 77°F., the composition and its thixotropic behavior, equipment such as areciprocating piston (positive displacement) pump, gear pump, pneumatictube (such as that supplied by SEMCO), caulking tube (hand trigger), airor airless spray, squeeze tube, brush, among other commerciallyavailable equipment, may be used. The uncured composition may then bemanipulated further, e.g., pressed or embossed, into a desired finish.

The inventive composition, once applied, is normally cured with asuitable, e.g., UV, radiation source. This can be done immediately uponapplication to a substrate, or delayed depending upon thecharacteristics desired in the coated substrate. For example, bydelaying the cure, the composition can be shaped, or leveled/smoothed tobetter conform to the underlying substrate. As aforementioned, the curemay be followed by a bake, or allowed to finish curing naturally. Thesealed joint or coated substrate may now be painted or otherwisefinished. If desired, one or more layers of compositions which arechemically similar or distinct can be applied upon a cured composition,e.g., two or more layers of UV cured composition can be appliedsequentially or used to form a laminate structure.

One method for applying the inventive composition is illustrated by theDrawings. Referring now to FIG. 1, FIG. 1 is a schematic diagram of arobotic means for applying the inventive composition; especially inautomotive applications such as a roof-ditch sealant. Robot 10 includesarm 11 that supports conduit 12. Examples of robots include thosesupplied by Fanuc, Inc., Rochester Hills, Mich., and ABB as ASEA Model2000. A means for providing UV radiation 13 can be supported by robotarm 11. The operation and movement of robot 10 and arm 11 are controlledand monitored by commercial computer means (not shown). The inventivecomposition is supplied under pressure via conduit 12 to any desiredlocation and in a virtually unlimited array of configurations. The lightintensity from means 13 and fluid flow rate through conduit 12 are alsocontrolled and monitored by commercially available computer means (notshown).

More details regarding one method for applying the inventive compositionare shown by FIG. 2. Referring now to FIG. 2, conduit 12 is in fluidconnection with dispensing or nozzle means 20. The inventive compositionis dispensed from nozzle means 20 and applied upon a surface 21 therebyforming coating or seal 22. The thickness and configuration of seal 22are determined by the pressure within conduit 12 and movement of arm 11.Substantially immediately after being dispensed, the composition isexposed to UV radiation from lamp means 13. The lamp means 13 anddispensing nozzle 20 are in fixed spatial relationship by connectingmeans 23 that is in turn affixed to arm 11. The UV exposed seal 22 is atleast partially cross-linked or cured thereby forming a self-supportingseal 22. While the entire thickness of seal 22 may not be cured, thecured portion of seal 22 is adequate to prevent the seal 22 from fluidflow. Uncured portions, if any, of seal 22 can become cured duringsubsequent heat treatments, e.g., if the seal 22 comprises a roof ditchthen residual curing will occur when exposed to high temperaturepainting processes.

While the above description emphasizes curing an epoxy containingcompound by exposure to a suitable radiation source, the inventivemethod can be achieved by employing other polymer systems such assilicones, urethanes, silanes, hydroxyl or caboxyl modified elastomers;hydroxyl, carboxyl or epoxy functional compounds, reactive liquidpolymers such as Hycar®, among others. That is, a polymer system whichwhen exposed to a suitable source of radiation including pre-iniatingcauses at least a portion of the system to cure.

The following Examples are provided to illustrate not limit the scope ofthe invention as defined by the appended claims. Unless indicatedotherwise, the materials and equipment discussed below are commerciallyavailable.

EXAMPLES

The exemplary compositions were obtained by blending its constituents.The following equipment was employed for blending the constituents:

1) Heated mixing Vessel of suitable volume (50-300 gal)

2) Mixer (Rotor-Stator, or Dispersion Blade, or Double Planetary Paddle)

3) Vacuum

4) Heated Liquid Pump

5) Unheated Liquid Pump

6) Weight Scale

7) Shipping Container Filling Equipment (Tube, Pail, or Drum)

Example 1

Blending began by pumping into the mixing vessel polyester polyol(Dynacoll 7110) at 250 F. One-hundred fifty-four pounds of a secondpolyester polyol (Tone 0301) was added to the mixing vessel. The polyolswere blended until both polyol constituents are fully dissolved in eachother. The polyol mixture is substantially transparent. The temperaturewithin the mixing vessel was maintained at 180 F.

One-hundred thirty-five pounds of cyclaliphatic epoxy (Uvacure 1500) wasthen added to the mixing vessel. When all of the epoxy was uniformlymixed, 3.3 pounds of sulfonium salt (UVI-6974) were added to the vessel.Mixing was continued at a temperature of 180 F. for 10 min.

Eleven pounds of silica (Cab-O-Sil) was then added to the mixing vessel.The silica was stirred into the mixture until wetted. Then another 11pounds of silica (Cab-O-Sil) is added. Mixing was continued to fullydispersed the constituents of the vessel. Mixing was then performed athigh shear rate under vacuum until substantially no lumps and no airbubbles were visible. It was important to eliminate all air bubbles, forthey may cause a discontinuity in the delivery line during customerapplication, and therefore an undesirable inconsistent delivery.

When vacuuming was completed, the resultant mixture was warm and clearwith a consistency of syrup. When the batch is cooled and the shearstresses diminished, the mixture was thickened to a near gel state whilemaintaining clarity. For best results, shipping or storage containersshould filled prior to cooling.

After the containers are filled and material cooled, specific gravityand viscosity checks should be performed to insure batch quality. Forbest results and in order to avoid premature curing of the composition,all storage and shipping containers should be opaque or shielded from UVsources including sunlight and fluorescent lighting. Such exposure couldresult in cure initiation thereby preventing the contents from beingpumped.

Example 2

One inventive composition was produced in accordance with the followingmethod. A two (2) gallon Ross Model PD2 planetary dispersion mixer wasobtained and in connected to a Chromolox heater. The dispersion mixerwas operated at a temperature of 190 F.

2824 grams of liquid polyol (Tone 0301) and 888 grams of the solidpolyol (7110) were introduced into the mixer and mixed for 10 minutes.Sixty (60) percent (240 grams) of the silica thickener (Cabosil suppliedby Cabot Corporation) was introduced into the mixer and the combinationwas mixed for another 10 minutes.

500 grams of epoxy (Uvacure 1500) and the remaining 40% (160 grams) ofthe silica were then added and mixed for 10 min. This was followed byadding 60 grams of the photoiniatitor (Cyracure 6974) and 2172 grams ofepoxy (UVACure 1500) to the mixer and mixed for 5 minutes. The contentsof the mixer were then mixed under vacuum for 10 minutes therebyproducing 1.3 gallons of the inventive composition.

Example 3

222 g of polyester polyol (Dynacoll 7110) at a temperature of 250 F.were poured into the a gallon can. About 706 g of a second polyesterpolyol (Tone 0301) were added to the first polyol. The polyols wereblended in a Rotor-Stator Mixer. This until both constituents are fullydissolved in each other. The mixture was transparent at this point. Thetemperature of this mixture was maintained at 180 F.

Approximately 618 g epoxy (Uvacure 1500) were admixed with the heatedmixture. When all epoxy was uniformly mixed, 15 g of photoiniator(UVI-6974) were added. Mixing continued at a temperature of 180 F. for10 min.

To the mixture, about 50 g of silica (Cab-O-Sil) were added. The mixturewas stirred until the silica was wetted into the mix. An addition 50 gof silica (Cab-O-Sil) was combined with the mixture while continuingmixing until the silica was fully dispersed.

The mixture was transferred to a vacuum chamber and maintained undervacuum until all bubbling ceased in the mixture. About ½ gallon of theinventive composition was obtained.

Example 4

The composition described by Examples 2 and 3 was applied to a metalsubstrate and cured in accordance with the instant Example. An ASEAModel 2000 Robot having a movable arm was employed to control theposition of a SEMCO Dispensing tube. Movement of the arm was controlledby a ASEA (ABB) computer and software. Approximately 12 oz. of theinventive composition was applied at 40 psig via a Pyles High Flow RobotGun that was mounted on the robot arm. The composition was dispensedthrough a round nozzle, approx. 1 cm. in diameter and cured subsequentlyby a shuttered UV lamp (1600 watt lamp) that was also attached to robotarm. A schematic drawing of this system is shown by aforementioned FIGS.I and 2.

The inventive composition was also applied from the robot arm by using aPyles 5 gal. unheated pump (instead of the SEMCO tube), to supply thecomposition. A Pyles “snuff back” gun Model #12000 series was alsosubstituted for the previously identified high flow gun. The gun alsoincluded a modified flattened nozzle that applied a ribbon stream ofcomposition upon the substrate.

Example 5

A UV curable composition comprising the following components wasprepared:

Wt. COMPONENT TRADE NAME SUPPLIER % Cycloaliphatic Epoxy Uvacure 1534UCB Radcure 87 Polyester Polyol Dynacoll 7250 Huls America 4 PhenoxyResin PKHM 85 Phenoxy Specialties 4 Silicon Dioxide Cab-O-Sil Cabot 4Sulfonium Salt Cyracure UVI 6974 Union Carbide 1

The composition was prepared in a Ross DB-2 mixer and in accordance withthe following method:

1. Add: 5405 Set temp. to 180 F Mix in the Ross Mixer for 10 grams of1534 minutes at lowest speed setting. 260 grams of Cabosil 2. Add: 270Temp. at 180 F Mix for 20 minutes at lowest grams of PKHM speed setting.85 270 grams of 7250 3. Add: 56 Temp. at 180 F Mix under vacuum for 20grams of 6974 minutes at lowest speed setting.

Example 6

A UV curable composition comprising the following components wasprepared:

COMPONENT TRADE NAME SUPPLIER Wt. % Cycloaliphatic Epoxy Uvacure 1534UCB Radcure 87 Polyester Polyol Dynacoll 7250 Huls America 4 PolyesterPolyol Tone 0301 Union Carbide 4 Silicon Dioxide Cab-O-Sil Cabot 4Sulfonium Salt Cyracure UVI 6974 Union Carbide 1

The composition was combined in a Ross mixer and in accordance with thefollowing method:

1. Add: 5405 grams Set temp. Mix for 10 minutes at lowest of 1534 to 180F speed setting. 260 grams of Cabosil 2. Add: 270 grams of Temp. at 180Mix for 20 minutes at lowest Tone 0301 speed setting. 270 grams of 72503. Add: 56 grams of Temp. at 180 F Mix under vacuum for 20 6974 minutesat lowest speed setting.

The temperate used for mixing in Examples 5 and 6 can range from about150 to at least about 190 F. Acceptable results can also be obtainedfrom formulations of Examples 5 and 6 that contain about 75 to about 95wt. % epoxy and up to about 10 wt. % polyol and resin.

Example 7

A UV curable composition comprising the following components wasprepared:

Wt. COMPONENT TRADE NAME SUPPLIER % Cycloaliphatic Epoxy Uvacure 1500UCB Radcure 45 Polyester Polyol Tone 0301 Union Carbide 29 PolyesterPolyol Dynacoll 7250 Huls America 12 Phenoxy Resin PKHP 200 PhenoxySpecialties 5 Polybutadiene Poly BD 605 Elf Atochem 6 Silicon DioxideCab-O-Sil Cabot 2 Sulfonium Salt Cyracure UVI 6974 Union Carbide 1

The composition was combined in a Ross DB-2 mixer and in accordance withthe following method:

1. Add: 2683 grams of 1500 Set temp. to 250. Mix for 60 minutes 1747grams of Tone 0301 at lowest speed 312 grams of PKHP 200 setting. 2.Add: 686 grams of 7250 Temp. at 200 F Mix for 20 minutes 375 grams ofPoly BD 605 at lowest speed 125 grams of Cabosil setting. 3. Add: 56grams of 6974 Temp. at 150 F Mix under vacuum for 20 minutes at lowestspeed setting.

Example 8

A UV curable material comprising the following components was prepared:

COMPONENT TRADE NAME SUPPLIER AMOUNT Cyclaliphatic epoxy Uvacure 1500UCB Radcure 73 wt. % Polyester polyol Tone 0301 Union Carbide 25Sulfonium Salt Cyracure UVI-6974 Union Carbide  1 Fluorinated SurfactantFluorad FC-171 3M  1

The composition was prepared by combining the Uvacure 1500 and Tone 0301in a mixing vessel. The mixture initially exhibited turbidity. Themixture was stirred until turbidity disappears and visually appearsclear. The UVI-6974 and the Fluorad FC-171 were added to the mixture.Mixing was continued until the components were completely dispersedwhich occurred in about two minutes. The mixture was subjected to avacuum to eliminate entrained air. The mixture was tested in accordancewith conventional procedures and possessed the followingcharacteristics:

Brookfield Viscosity 300-400 cps @ 20° C. Hardness: Shore ‘A’-95-100Shore ‘D’->70 Shrinkage: Zero

One desirable characteristic of this composition is that it can beapplied to a substrate via spraying, e.g., by using a commerciallyavailable air or airless spray gun.

Example 9

A UV curable gel comprising the following components was prepared:

Gel A COMPONENT TRADE NAME SUPPLIER AMOUNT Cycloaliphatic Uvacure 1500Radcure 47 wt. % epoxy UCB Bis-F epoxy Epalloy 8230 CVC SpecialtyResings 10 Polyester Tone 0301 Union Carbide 36 polyol Sulfonium saltUVI 6974 Union Carbide 2 Silicon dioxide Cab-O-Sil TS-720 Cabot 5

Gel A was prepared by mixing the Uvacure, Epalloy, and Tone together ina mixing vessel until the solution was clear. The UVI 6974 was added,and mixed until the components were dispersed (about 2 minutes). TheCab-O-Sil was added to the mixture to function as the gelling agent, andmixed until substantially lump-free. A vacuum was applied to the mixtureuntil substantially all the air was removed (27 mm Hg, 10 minutes).

Gel B COMPONENT TRADE NAME SUPPLIER AMOUNT Cycloaliphatic epoxy Uvacure1500 Radcure 54 wt. % Polyester polyol Tone 0301 Union Carbide 38Sulfonium salt UVI-6974 Union Carbide 2 Silicon dioxide Cab-O-Sil M5Cabot 4 Surfactant Texaphor Special Henkel 2

Gel B was prepared by mixing the Uvacure and Tone together in a mixingvessel until the solution was clear. The UVI 6974 was added, and mixeduntil the components were substantially dispersed (about 2 minutes). TheCab-O-Sil was added to the mixture and mixed until substantiallylump-free. A vacuum was applied to the mixture until substantially allof the air was removed (27 mm Hg, 10 minutes). Mixture was gel-like, butwas not self-supporting. A gelling agent comprising a surfactant wasadded to the gel-like mixture. A gel, thereafter, formed rapidly.

Gel C COMPONENT TRADE NAME SUPPLIER AMOUNT Cycloaliphatic epoxy UVACURE1500 Radcure 87 wt. % Sulfonium salt UVI 6974 Union Carbide 1 Silicondioxide Cab-O-Sil M5 Cabot 3 Polyether Polyol LG 650 Arco 9

Gel C was prepared by mixing the Uvacure and polyol together in a mixingvessel until solution is clear. The UVI 6974 was added, and mixed untilsubstantially dispersed (about 2 minutes). The Cab-O-Sil was added tomixture and mixed until the mixture was substantially lump free. Avacuum was applied upon the mixture until substantially all of the airwas removed (27 mm Hg, 10 minutes).

The following Table lists the Brookfield Viscosity Data for Gels A, Band C (cps, in thousands) measured at 20 C using a number 6 spindle as afunction of revolutions per minute (RPM).

RPM Gel A Gel B Gel C 0.5 436 376 160 1 242 198 98 2.5 118 80 45 5 68.844 36 10 41.6 25.2 21 20 25.7 14.6 13.7 50 14.3 7.9 9.2 100 9.58 4.885.9

Example 10

A UV curable foam having the following components was prepared:

COMPONENT TRADE NAME SUPPLIER AMOUNT Cycloaliphatic epoxy UVACURE 1500Radcure 50 wt. % Polyester polyol Tone 0301 Union Carbide 40 Mechanicalblowing Expancel DU551 Nobel 9 agent Sulfonium salt UVI-6974 UnionCarbide 1

The above components were combined as follows. The Uvacure and polyolwere added together in a mixing vessel and mixed until the solution wasclear. The UVI 6974 was added to the mixture, and mixed untilsubstantially completely dispersed (about 2 minutes). The Expancelsspheres were added to the mixture and mixed until substantially lumpfree. For best results, the minimum amount of mixing time, and shearwere employed.

Example 11

A UV curable composition comprising the following components wasprepared:

COMPONENT TRADE NAME SUPPLIER AMOUNT Cycloaliphatic epoxy Uvacure 1500UCB Radcure 31 wt. % Bis-F epoxy Epalloy 8230 CVC Specialty 11 ResingsPolyester polyol Tone 0301 Union Carbide 33 Polyester polyol Dynacoll7110 Huls America 21 Sulfonium salt UVI 6974 Union Carbide 2 Silicondioxide Cab-O-Sil TS-720 Cabot 2

This composition was prepared by heating the Uvacure, Epalloy, Dynacoll,and Tone together in a mixing vessel at a temperature of 180 F. Thematerials were mixed until the solution was clear. The UVI 6974 wasadded, and mixed until the components were dispersed (about 2 minutes).The Cab-O-Sil was added to the mixture and mixed until substantiallylump-free. A vacuum was applied to the mixture until substantially allthe air was removed (27 mm Hg, 10 minutes).

This composition was applied onto a bent 4×12 inch that had been coatedwith an automotive E-Coat, exposed to UV light, painted white, baked andthen subjected to a South Florida Inland, 5° South, Direct WeatheringExposure to determine the microbial resistance of this composition.After periods of three months, six months, twelve months and twenty-fourmonths, no mold, mildew or other microbe growth was detected by visualobservation.

Example 12

This Example illustrates a two component system that can be producedwithout radiation curing. The composition was obtained by contactingPart “A” with Part “B”. Part “A” and Part “B” were pre-blended in amixer and contacted by static mixer. The resulting composition waspumpable, paintable and can be employed for repairing damaged paintedsurfaces, e.g, an automotive body panel. The following tables list thecomponents of Part A and Part B.

TRADENAME COMPONENT AMOUNT Part A Uvacure 1500 cycloaliphatic epoxy 35Dynacoll 7110 polyol 10 Cab-O-Sil M5 silica powder 5 Part B Tone 0301polyol 35 Dynacol 7110 polyol 10 Cab-O-Sil silica powder 3 commodityphosphoric acid 2

Example 13

This Example illustrates using a robotic means for applying a UV curablematerial within an automotive roof ditch in order to seal the underlyingweld. The UV curable composition of Example 5 was dispensed into anautomotive roof ditch by a computer controlled robot by using a Pyles 5gallon, reciprocating piston, positive displacement pump, SECOtemperature controlled metering system and snuff back robot gun. Tworobots were used for this application trial: a) Fanuc model F500 wasemployed to dispense the composition into the ditch and b) a Fanuc model420i was employed to transport a UV light source along the ditch to curethe composition. The UV light source comprised a Fusion Systems modelT-6,500 watts/inch, 6 inch bulb, H type, mounted on the arm of the model420i so that the UV bulb ran parallel to ditch. The composition wasdispensed at a rate of 250 mm/sec and the UV light was passed over thedispensed composition at a rate of 250 mm/sec; for a total applicationand cure time of 30 seconds. The material was applied at ambienttemperatures.

The following process steps were used to dispense and cure thecomposition:

1. Cure robot start position was directly behind a “D” pillar end of theroof ditch with UV light on.

2. The dispensing robot moved to an initial position (positioned 3 to 5mm directly above the ditch) approximately 18 inches in front of the endof the ditch (between D and C pillar).

3. The UV curable composition was applied into the ditch moving towardthe D pillar. Material was applied to within 8 to 15 mm of the end ofthe ditch, at which time the dispensing robot moves up and away from theditch.

4. The cure robot immediately started moving along the length of theditch starting at the D pillar and moving forward. Meanwhile, thedispensing robot moved back to its original starting point (3 to 5 mmdirectly above the ditch approximately 18 inches in front of the end ofthe ditch) and applied material in the ditch while moving forward.

5. At this point, both robots moved in tandem forward along the ditch.The distance between the dispensing gun and lamp housing wasapproximately 6 to 8 inches.

6. The dispensing robot applied material in the ditch to within 8 to 15mm of the front of the ditch (A pillar) and immediately moved up andaway from the ditch.

7. The cure robot continued movement to the front of the ditch (Apillar) and immediately reversed direction, traveling back the entirelength of the ditch and stopping at its original start position

8. The UV light was turned off and a self-supporting layer was formed inthe ditch.

Example 14

This Example illustrates adding a silane compound to the curablecomposition of Example 5 for improving paint adhesion, high temperatureresistance, e.g., to temperatures of greater than 340 F., among otherproperties.

A curable composition having the following components was prepared:

COMPONENT Trade Name Supplier Wt. % Cycloaliphatic Uvacure 1534 UCBRadcure 86 Epoxy Polyester Polyol Dynacoll 7250 Huls America 4 PhenoxyResin PKHM 85 Phenoxy 4 Specialties Silicon Dioxide Cab-O-Sil Cabot 4Sulfonium Salt Cyracure UVI Union Carbide 1 6974 Silane Z-6040 DowCorning 1

The above composition was prepared in a Ross DB-2 mixer and inaccordance with the following method:

1. Add: 4600 grams of 1534 Set temp. to 180 F. Mix in the  230 grams ofCabosil Ross Mixer for 10 minutes at lowest speed setting. 2. Add: 230grams of PKHM 85 Temp. at 180 F. Mix for 20 230 grams of 7250 minutes atlowest speed setting. 3. Add: 51.5 grams of 6974 Temp, at 180 F. Mixunder 51.5 grams of Z-6040 vacuum for 20 minutes at lowest speedsetting.

The mixed composition was applied onto a 4′×12′ ED5100 Electro-paintedtest panel and cured by exposure to UV light in accordance with Example13. The cured composition was coated with a powder primer paint.

The powder paint comprised PCBV70100M supplied by PPG, Pittsburgh, Pa.The paint was applied in accordance with conventional practice by usingan Eastwood Company applicator (HotCoat coating system part no. 1980).The powder paint coated test panel was baked within one hour ofapplication at 340 F. for 20 minutes. The panel inspected visually andwas uniformly coated with no visual defects.

Example 15

This Example illustrates a pigment containing curable composition. Thecomposition of Example 14 was modified by adding a pigment, E2557 green(or other color supplied by Akrochem). The curable material was appliedand processed as in Example 14.

Example 16

This Example illustrates a radiation curable composition that can besprayed upon a substrate and subsequently cured. The followingcomposition was prepared in accordance with the method of Example 14.

COMPONENT TRADE NAME SUPPLIER AMOUNT Cyclaliphatic epoxy Uvacure 1500UCB Radcure 47 wt. % Polyester polyol Tone 0301 Union Carbide 36Sulfonium Salt Cyracure Union Carbide 1 UVI-6974 Fluorinated SurfactantFluorad FC-171 3M 1 Bis F epoxy Epalloy 8230 CVC Specialties 15

The above composition was sprayed at a pressure of 80 psi by using aDeVilibis type MBC spray gun onto a painted substrate. The substratecomprised a commerically available automobile body panel that had beenpainted with tan DuPont Centari Acrylic Enamel. The sprayed coating wascured by exposure to naturally occurring UV radiation.

This composition can be employed in a wide range of end-uses includingupon a previously painted surface, e.g. an automotive body panel, forimproving abrasion resistance, among other properties of the paintedsurface.

In an alternative embodiment of this Example, a temporary or removablecoating can be applied onto a substrate. The coating can be applied ontoa painted surface and, thereafter, either be removed or replaced. Thistype of coating can be obtained by either applied a surface tensionagent, e.g., a commercially available wax or surface protectant, or byadding a relatively high amount of a surfactant, e.g., bis-F epoxy, tothe sprayable composition. The removable spray composition can beapplied onto a painted or unpainted surface in order to impart temporaryprotection, e.g., from extreme environment conditions, road hazards,transportation, etc., and, thereafter, removed or reapplied as desired.

Example 17

This Example illustrates a method for using the UV curable compositionformed in accordance with Example 14 to repair surface damage to ametallic surface. The repaired surface can be painted or re-painted.

PROCEDURE 1: Repair of dent, defect or hole in a metal panel

A substrate comprising a commercially available ED5100 laboratory testpanel was cleaned with an alcohol/naptha containing wipe and coated inaccordance with conventional methods with a DuPont 30S primer and DuPontCentari Acrylic Enamel (OEM recommendations or equivalent Body shopmaterials should be used).

The UV curable composition was applied by hand/brush and cured by beingexposed to UV light so as to provide the curable composition protrudingabove intended repair area. The UV curable composition can be layered toachieve proper depth where required.

After being exposed to UV radiation, the cured composition was allowedto continuing curing under ambient conditions for a period of 3-4 Hrs.The cured composition was then sanded by hand with 180 through 360 gritsandpaper. The sanded surface was then coated with the aforementionedprimer and paint.

Infared or convection heat sources can be used, if desired, for reducingthe post cure time, e.g., about 150 to about 200 F.

PROCEDURE 2: Repair of existing sealer in seam.

The sealant applied in accordance with Example 14 was removed bysanding. The damaged area was cleared of dust or any other residue, andcleaned with an alcohol/naptha wipe (any other suitable cleaner can beemployed). The UV composition was applied by hand/brush and cured bybeing exposed to UV light so as to provide the sealer protruding abovethe surrounding area.

After being exposed to UV radiation, the cured composition was allowedto continuing curing under ambient conditions for a period of 3-4 Hrs.The cured composition was then sanded by hand with 180 through 360 gritsandpaper. The sanded surface was then coated in turn DuPont 30S primerand DuPont Centari Acrylic Enamel.

Infared or convection heat sources can be used, if desired, for reducingthe post cure time, e.g., about 150 to about 200 F.

These Examples demonstrate that the inventive composition and method canbe employed for repairing a damaged automotive body panel.

Example 18

This Example demonstrates a UV curable material that is subsequentlybaked at a temperature of about 200 to 300 F.

COMPONENT TRADE NAME SUPPLIER AMOUNT cycloaliphatic epoxy Uvacure 1500UCB Radcure 47.9 wt % polyether polyol PPG-725 Lyondell 45.6 sulfoniumsalt UVI-6974 Union Carbide  0.5 photoinitiator treated fumed silicaAerosil R202 Degussa  1 treated fumed silica Aerosil R805 Degussa  5

The liquid components of the composition were combined within the mixingapparatus described in Example 14. The silicas were added to the liquidmixture and mixed until dispersion was completed. The mixed compositionwas then applied to commercial automotive Ecoated panels (Coremax EP)and cured with an HP-6 High-powered UV Lamp System (Fusion UV Systems,Inc.) using a “D” bulb. The “D” bulb has a UV output of varyingintensities in a wavelength range from about 200 nm to about 600 nm. Thecomposition was fully cured after exposure to a depth of approximately0.5 inch (the depth of cure can vary depending on the UV source and thedistance of the source from the material). The UV cured composition onthe ECoat panel was baked in a 200-300° F. oven to further cure thecomposition (alternatively, the UV cured composition can be allowed tocure further under ambient conditions). The cured composition adhered tothe e-coated metal as evidenced by continued adhesion of the ecoatmaterial to the UV material when the metal panel is bent in half.

Example 19

This is a variation of the composition in Example 18 which retains thesame epoxy to hydroxy ratio, henceforth known as the EHR. The EHR is theratio of the number of epoxy groups in the formulation to the number ofhydroxy groups present. Typical EHRs for the inventive composition canrange from 20 to 2, depending on the raw materials used.

COMPONENT TRADE NAME SUPPLIER AMOUNT Cycloaliphatic epoxy Uvacure 1500UCB Radcure 44 wt % Polyether Polyol PPG-3025 Lyondell 11 PolyetherPolyol PPG-725 Lyondell 39 Sulfonium Salt UVI-6974 Union Carbide 0.5Photoinitiator treated fumed silica Aerosil R202 Degussa 0.5 treatedfumed silica Aerosil R805 Degussa 5

Mixing, dispensing and curing of this formula was performed inaccordance with Example 18.

The paintability of the cured compositions formed in Examples 18 and 19was tested by applying commercial automotive primer (DuPont White), thenbaking at the recommended time and temperature. This was followed by acoat of commercial basecoat (DuPont Toreador Red), which was also bakedaccording to the recommended parameters. Testing for adhesion wasperformed according to a modified version of GM9071P, the General Motorsspecification for “Tape Adhesion Test for Paint Finished.” The curedcompositions of Examples 18 and Example 19 remained paintable, asdetermined by GM9071P, even after storage for 48 hours at 100%condensing humidity.

The Shore A Durometer Hardness of aged and cured compositions formed inExamples 18 and 19 was measured in accordance with conventional methods.The cured compositions were aged for 48 hours in room temperature (RT),and 48 hours in 100% relative humidity (RH). The results of the Shore Ameasurements are listed below.

Shore A Durometer Values Formula Storage Shore A Example 18 RT, 48 hrs.88 Example 19 RT, 48 hrs. 89 Example 18 100% RH, 48 hrs. 85 Example 19100% RH, 48 hrs. 85

Example 20

This Example illustrates a UV curable composition having a decreasedEHR.

COMPONENT TRADE NAME SUPPLIER AMOUNT cycloaliphatic epoxy Uvacure 1500UCB Radcure 43.7 wt % polyether polyol PPG-725 Lyondell 49.7 sulfoniumsalt UVI-6974 Lyondell 0.6 photoinitiator treated fumed silica AerosilR202 Degussa 1 treated fumed silica Aerosil R805 Degussa 5

This composition was mixed, dispensed and cured in accordance with themethod of Example 18.

Example 21

This Example illustrates a UV curable composition having a decreasedEHR.

COMPONENT TRADE NAME SUPPLIER AMOUNT cycloaliphatic epoxy Uvacure 1500UCB Radcure 38.6 wt % polyether polyol PPG-725 Lyondell 54.9 sulfoniumsalt UVI-6974 Union Carbide 0.5 photoinitiator treated fumed silicaAerosil R202 Degussa 1 treated fumed silica Aerosil R805 Degussa 5

This composition was mixed, dispensed and cured in accordance with themethod of Example 18.

Example 22

This Example demonstrates a UV curable composition having an increasedtensile strength. This Example also illustrates a composition having anincreased EHR.

COMPONENT TRADE NAME SUPPLIER AMOUNT cycloaliphatic epoxy Uvacure 1500UCB Radcure 62.4 wt % polyether polyol PPG-725 Lyondell 31.1 sulfoniumsalt UVI 6974 Union Carbide 0.5 photoinitiator treated fumed silicaAerosil R202 Degussa 1 treated fumed silica Aerosil R805 Degussa 5

This composition was mixed, dispensed and cured in accordance with themethod of Example 18. Tensile strengths for cured compositions formed inaccordance with Examples 18-22 were tested and determined according toASTM D638-96.

Avg. Tensile Strength Composition (lb/in²) Example 18 805 Example 19 682Example 20 376 Example 21 223 Example 22 3,256

The following two examples (Examples 23 and 24) illustrate the additionof a non-functional resin as a component of the UV curable composition.When added in an effective amount, this resin functions as a toughenerand/or flexibilizing agent.

Example 23

COMPONENT TRADE NAME SUPPLIER AMOUNT cycloaliphatic epoxy Uvacure 1500UCB Radcure 42.5 wt % polyether polyol PPG-725 Lyondell 41ethylene-vinyl acetate Elvax 46 DuPont 10 copolymer resin sulfonium saltUVI-6974 Union Carbide 0.5 photoinitiator treated fumed silica R202Degussa 1 treated fumed silica R805 Degussa 5

The EVA copolymer resin was heated in a tin to a temperature of about201° F. with an amount of the polyol sufficient to soften the EVA. Whilecontinuing to heat, the EVA copolymer was stirred into the polyol.Heating continued as the rest of the polyol was stirred in gradually.When the polyol/EVA mixture had cooled to a temperature of about 80° F.,the cycloaliphatic epoxy was added with stirring. When the addition ofthe epoxy was completed, the silicas were stirred into the mixture untilcompletely dispersed. The mixed composition was then dispensed and curedin accordance with the method of Example 18.

Example 24

This composition was mixed, dispensed and cured in accordance with themethod of Example 23.

COMPONENT TRADE NAME SUPPLIER AMOUNT cycloaliphatic epoxy Uvacure 1500UCB Radcure 44.5 wt % polyether polyol PPG-725 Lyondell 44ethylene-vinyl acetate Elvax 46 DuPont 5 sulfonium salt UVI-6974 UnionCarbide 0.5 photoinitiator treated fumed silica R202 Degussa 1 treatedfumed silica R805 Degussa 5

The tensile strength and percent elongation of the cured compositionsformed in accordance with Examples 18-24 were determined. Tensilestrengths, calculated according to ASTM D638-96, and percent elongationvalues are listed below. The percent elongation was calculated bydividing the displacement at maximum tensile load by the original gaugelength. This value was then multiplied by 100.

Composition Avg. Tensile (lb/in²) % elongation Example 18 805 49 Example19 682 45 Example 22 1113 56 Example 23 745 49

The following examples illustrate two-part systems that utilize acationic type cure chemistry.

Example 25

COMPONENT TRADE NAME SUPPLIER AMOUNT Part A Cycloaliphatic epoxy Uvacure1500 UCB Radcure 28.3 wt % polyether polyol PPG-3025 Lyondell 51.8polyether polyol PPG-725 Lyondell 13.7 sulfonium salt UVI-6974 UnionCarbide 1.1 photoinitiator treated fumed silica R805 Degussa 5.1 Part BCycloaliphatic epoxy Uvacure 1500 UCB Radcure 26 wt % polyether polyolPPG-3025 Lyondell 47 polyether polyol PPG-725 Lyondell 12.8 treatedfumed silica R805 Degussa 4.7 Ground 9.5 Polyethylene

The liquids of Part A are mixed, and the silica added and dispersed inaccordance with the method described in Example 18. The liquids of PartB are similarly mixed and the silica added. A UV-opaque filler, groundpolyethylene, was then mixed into Part B.

Part A was activated by exposing it to UV radiation from a suitablesource. Part A and Part B were then mixed together in a tin by hand, andallowed to cure.

Worktime (WT) of the activated compositions was measured in minutes andseconds at defined intervals by ascertaining when the activatedcomposition began to harden or increase in viscosity. WT is given inminutes (′) and seconds (″). The worktime of the activated compositioncan be adjusted by the dosage or wavelength of UV radiation it receives.Below is a table listing the worktimes obtained with Parts A and B abovewhen they were irradiated at three (3) UV exposures which gave thedosages (Joules/cm²) listed below.

Approximate Dosages (Joules/cm²) WT UVA UVB UVC UVV 17′ 0.230 0.1520.015 0.108  1′56″ 0.334 0.242 0.026 0.175  1′40″ 0.465 0.310 0.0320.259

The above table illustrates that the worktime (WT) decreases as the UVdosage is increased.

Example 26

This Example illustrates a two component UV curable composition having apre-iniated component.

COMPONENT TRADE NAME SUPPLIER AMOUNT Part A Polyether polyol PPG-725Lyondell 92.8 wt % Sulfonium salt UVI-6974 Union Carbide 1.1photoinitiator treated fumed silica R202 Degussa 1.1 treated fumedsilica R805 Degussa 5 Part B Cycloaliphatic epoxy Uvacure 1500 UCBRadcure 94 wt % Treated fumed silica R202 Degussa 1 Treated fumed silicaR805 Degussa 5

The cycloaliphatic epoxy was confined or isolated to one side of thesystem, (Part A), while the photoinitiator and polyol (non-reactivewithout the epoxy) were present only in Part B. Without wishing to bebound by any theory or explanation, it is believed that the UV-exposedphotoinitiator should remain active for a relatively long period of timesince it does not react with the polyol. Part A was prepared inaccordance with accordance with the method described in Example 18, andirradiated with the UV source also described in Example 18, then mixedwith Part B by hand. A reaction between the Part A and Part B occurredin 0.25-0.5 minutes.

A portion of Part A was irradiated with the UV radiation, but this time5 minutes were allowed to pass before mixing with Part B. A reactiontook place within 0.5 minutes.

Another portion of Part A was exposed to the UV radiation, but allowedto remain undisturbed for 1 hour before mixing with Part B. Reactiontook place within 42 seconds.

Example 27

This Example illustrates a two component system having at least onepre-initiated component and dispensing the components through a statictube mixer.

COMPONENT TRADE NAME SUPPLIER AMOUNT Part A Polyether polyol PPG-725Lyondell 92.8 wt % Sulfonium salt UVI-6974 Union Carbide 1photoinitiator treated fumed silica R202 Degussa 1.1 treated fumedsilica R805 Degussa 5.1 Part B Cycloaliphatic epoxy Uvacure 1500 UCBRadcure 46.2 wt % Ground silica Goresil 1045 C.E.D. 53.8 ProcessedMinerals, Inc.

Part A was prepared in accordance with the methods described in Example18 and exposed to light from the UV source described in Example 18 (UVAdosage=approx. 3.8 J/cm²) and loaded into one side of a static mixercartridge (commercially available from Mixpac). Part B was prepared inaccordance with Example 18, and loaded into the other side of the staticmixer cartridge. When extruded through a static mixing tip, the materialcured within 1 minute. The material in the cartridge was extrudedthrough a static mixer 4 hours later and cured within 1 minutes. Twodays later, these pre-initiated materials were mixed and cured within 2minutes.

Example 28

This Example illustrates a pre-iniated composition, and worktime of thecomposition as a function of time after being pre-iniated.

COMPONENT TRADE NAME SUPPLIER AMOUNT Part A Polyether polyol PPG-725Lyondell 94.8 wt % Sulfonium salt UVI-6974 Union Carbide 1.1photoinitiator treated fumed silica R202 Degussa 4.1 Part BCycloaliphatic epoxy Uvacure 1500 UCB Radcure 96.0 wt % treated fumedsilica R202 Degussa 4.0

Part A and Part B were prepared in accordance with the methods describedin Example 18. Part A was irradiated with the UV source described inExample 18 to give a UVA dosage≡3.8 J/cm². Part A and Part B wereweighed and mixed by hand. The worktime in minutes and seconds wasdetermined visually as the first sign of color and thickening of themixture. The weighing and worktime evaluation was conducted over aperiod of several days to determine how long the irradiatedphotoinitiator remained active.

Days after Part A Part B UV exposure weight (g) weight (g) Worktime 01.01 1.05 45″ 1 1.01 1.06 40″ 2 1.05 1.04 41″ 3 1.06 1.05 46″ 4 1.021.03 48″ 7 1.01 1.01 56″ 8 1.05 1.05 59″ 9 1.05 1.04  1′05″ 10 1.03 1.0455″ 14 1.03 1.02  1′19″ 15 1.02 1.04  1′23

A skilled person in this art would understand that these Exemplaryprocesses can be modified by manipulating process variables such as timeand temperature of each aforementioned mixing step, mixing rate (RPM),time under vacuum, amount and type of energy source, and level of vacuum(mm Hg) as well as operating a continuous process. While the aboveExamples illustrate a batch process a skilled person in this art afterhaving reviewed and understood the instant disclosure, would be capableof manipulating the aforementioned process variables to tailor theinstant composition for a virtually unlimited array of productapplications.

While the present invention has been described in certain preferredembodiments thereof, it will be apparent that various substitution,omissions, modifications, and other changes which may be made withoutdeparting from the spirit of the invention. Thus, the present inventionshould be limited only by the scope of the following claims includingequivalents thereof.

What is claimed is:
 1. A method for providing a cured coating on asubstrate comprising at least one member selected from the groupconsisting of metal, wood, concrete and cement from a compositioncomprising a combination comprising at least one epoxy functionalcompound, greater than about 0.1 wt % and less than 20 wt % of at leastone of ethyl vinyl acetate and copolymers thereof, and at least onephotoinitiator wherein said method comprises: (a) exposing at least onecomponent of the composition to a source of radiation; and (b) applyingthe composition onto a substrate thereby forming a coating upon thesubstrate.
 2. The method according to claim 1 wherein the substratecomprises metal and the coating overlies a joint between at least twometal substrates.
 3. The method according to claim 2 wherein the jointis formed by welding together at least two automotive body components.4. The method according to claim 1 further comprising (c) heating thecoated substrate to a temperature sufficient to improve adhesion of thecomposition to the substrate.
 5. The method according to claim 1 whereinthe epoxy compound comprises a cycloaliphatic epoxy compound.
 6. Themethod according to claim 1 wherein the combination further comprises apolyether polyol, a polyester polyol or mixture thereof.
 7. Thecomposition according to claim 1 wherein the photoinitiator comprises aUV photoinitiator.
 8. The method according to claim 7 wherein theradiation comprises ultraviolet radiation.
 9. The method according toclaim 1 wherein the photoinitiator comprises an onium salt.
 10. Acomposition comprising a combination comprising: (a) about 40 to about90 wt. % of at least one epoxy functional compound; (b) at least onemember selected from the group consisting of ethyl vinyl acetate andcopolymers thereof; (c) at least one polyol wherein the ratio of said atleast one epoxy functional compound to said at least one polyol isgreater than 1:1 to about 2:1; and (d) al least one photoinitiator. 11.The composition according to claim 10 wherein the epoxy compoundcomprises a cycloaliphatic compound.
 12. The composition according toclaim 10 wherein the polyol comprises a polyester polyol, polyetherpolyol or mixture thereof.
 13. The composition according to claim 10wherein the photoinitiator comprises a UV photoinitiator.
 14. Thecomposition according to claim 13 wherein the photoinitiator comprisesan onium salt.
 15. The composition according to claim 10 furthercomprising (d) a thickening agent.
 16. The composition according toclaim 15 wherein the thickening agent comprises silica.
 17. Thecomposition according to claim 15 wherein the thickening agent ispresent in amount effective to provide a thixotropic composition. 18.The composition according to claim 15 further comprising (e) at leastone monomeric material.
 19. The composition according to claim 18further comprising (f) at least one gelling agent.
 20. The compositionaccording to claim 10 wherein the ratio of epoxy compound to polyol isabout 1:1 to about 2:1.
 21. A method of providing a self supportingarticle or layer comprising: (a) providing a first component comprisingat least one epoxy functional compound, find a second componentcomprising at least one acid source, with at least one of the firstcomponent and second component comprising ethyl vinyl acetate andcopolymers thereof, and (b) combining the first and second components soas to react the epoxy functional compound with the acid source.
 22. Themethod according to claim 21 further comprising (c) introducing thereaction product of (b) onto a substrate.
 23. The method according toclaim 21 wherein both of the first and second components furthercomprises at least one polyol.
 24. A composition for forming aself-supporting article or layer comprising: (a) a first componentcomprising at least one epoxy functional compound, and (c) a secondcomponent comprising at least one acid source, wherein at least one ofthe first and second component comprises ethyl vinyl acetate andcopolymers thereof.
 25. The method of claim 1 wherein said exposing issufficient to increase the viscosity of the composition.
 26. Acomposition for forming a self-supporting article or layer comprising:(a) a first component comprising at least one epoxy compound, and (b) asecond component comprising at least one acid source, wherein at leastone of the first and second component comprises at least one polyol andat least one member selected from the group consisting of ethyl vinylacetate and copolymers thereof.
 27. The composition according to claim26 wherein both the first and second components further comprise atleast one polyol.
 28. A composition according to claim 26 wherein thepolyol comprises a polyester polyol, the epoxy compound comprises acycloaliphatic epoxy compound, and the acid comprises phosphoric acid.29. The composition of claim 10 wherein said at least one epoxyfunctional compound comprises at least one cycloaliphatic epoxy and saidat least one polyol comprises at least one polyether polyol, and furthercomprising silica.
 30. The composition of claim 10 further comprises atleast one member from the group consisting of acrylates, caprolactones,and polycarbonates.
 31. The method of claim 1 wherein said substratecomprises at least one member from the group consisting of e-coatedarticles, brake rotors, fasteners, end-fittings and couplings.
 32. Themethod of claim 1 wherein said applying comprises at least one methodfrom the group consisting of spraying and immersing.
 33. The compositionof claim 10 wherein said composition further comprises at least onemember chosen from the group consisting of silicones, urethanes, silanesand hydroxyl or caboxyl modified elastomers.
 34. The composition ofclaim 10 wherein said composition is substantially free of polyvinylchloride and volatile organic compounds (VOCs).
 35. The method of claim3 wherein said joint comprises a roof ditch.
 36. A compositioncomprising a combination comprising: (a) at least one epoxy functionalcompound; (b) at least one member selected from the group consisting ofethyl vinyl acetate and copolymers thereof; (c) greater than 40 wt. % ofat least one polyol; and (d) at least one photoinitiator.
 37. Thecomposition of claim 36 further comprising at least one hydroxyl orcaboxyl modified element.
 38. A method for sealing a weld between atleast two metallic substrates with a composition comprising acombination comprising at least one epoxy functional compound, at leastone of ethyl vinyl acetate and copolymers thereof, at least one polyoland at least one photoinitiator wherein said method comprises: (a)applying the composition onto the substrate, (b) exposing at least aportion of the composition to at least one source of radiation; (c)heating at least a portion of the radiation exposed composition.
 39. Themethod of claim 38 wherein the substrate comprises automotive componentsand said welded connection comprises a roof ditch.
 40. The method ofclaim 38 wherein said source of radiation comprises UV.
 41. The methodof claim 38 wherein said polyol comprises at least one polyether polyol.42. The method of claim 39 wherein said composition further comprisessilica.
 43. The composition of claim 26 wherein said second componentfurther comprises at least one of ethyl vinyl acetate and copolymersthereof.
 44. A method for providing a coating on a substrate comprisingat least one member selected from the group consisting of metal, wood,concrete and cement from a composition comprising a first component anda second component wherein at least one of said first and secondcomponents comprise at least one epoxy functional compound, at least onepolyol, at least one thickener, and at least one photoinitiator whereinsaid method comprises: (a) exposing at least one of said first andsecond components to a source of UV radiation; (b) combining the firstand second components; and (c) applying the combined first and secondcomponents onto the substrate thereby forming a coating upon thesubstrate.
 45. The method according to claim 21 further comprisingapplying the first and second components onto a substrate comprising atleast one member selected from the group consisting of metal, wood,concrete and cement.